KR102685764B1 - Organic electroluminescent materials and devices - Google Patents

Abstract

In this application, novel organic compounds containing indolocarbazole and fluorene moieties are disclosed. The compounds are suitable for applications in organic electroluminescent devices.

Description

Organic electroluminescent materials and devices {ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES}

Cross-reference to related applications

This application is related to U.S. Provisional Application Nos. 62/143,370 filed on April 6, 2015, 62/245,578 filed on October 23, 2015, 62/254,299 filed on November 12, 2015, and Priority is claimed on No. 62/274,520, filed January 4, 2016, the entirety of which is incorporated herein by reference.

Parties to joint research agreements

The claimed invention was made by, for, and/or in association with one or more of the following parties pursuant to a joint industry-academic research agreement: Regents of the University of Michigan; Princeton University, University of Southern California, and Universal Display Corporation. This Convention is in effect on and before the date on which the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of the Convention.

Field of the invention

The present invention relates to compounds for use as host materials or electron transport materials and devices comprising them, such as organic light emitting diodes.

Optoelectronic devices using organic materials are becoming increasingly important for several reasons. Because many of the materials used to make such devices are relatively inexpensive, organic optoelectronic devices have the potential for a cost advantage over inorganic devices. Additionally, the unique properties of organic materials, such as their flexibility, may make them well suited for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaics, and organic photodetectors. In the case of OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which an organic emitting layer emits light can generally be easily adjusted with appropriate dopants.

OLEDs use thin organic films that emit light when a voltage is applied across the device. OLED is an increasingly important technology for applications such as flat panel displays, lighting and backlighting. Various OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emitting molecules is full color displays. Industry standards for such displays require pixels to be tuned to emit specific colors, referred to as “saturated” colors. In particular, these criteria require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In a typical flat panel liquid crystal display, the emission from the white backlight is filtered using an absorption filter to produce red, green, and blue emissions. The same technique can also be used for OLED. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art.

One example of a green emitting molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy) ₃ and having the formula:

In this and the following formulas herein, the Applicant depicts the coordination bond from nitrogen to metal (here Ir) as a straight line.

As used herein, the term “organic” includes small molecule organic materials as well as polymeric materials that can be used to fabricate organic optoelectronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” can actually be quite large. Small molecules may contain repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not exclude the molecule from the “small molecule” category. Small molecules can also be incorporated into the polymer, for example as pendant groups on or as part of the polymer backbone. Small molecules can also act as the core moiety of dendrimers, which consist of a series of chemical shells built on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be “small molecules,” and all dendrimers currently used in the OLED field are believed to be small molecules.

As used herein, “top” means furthest from the substrate and “bottom” means closest to the substrate. When a first layer is described as being “disposed on top” of a second layer, the first layer is disposed at a distance from the substrate. There may be other layers between the first and second layers unless it is specified that the first layer is “in contact” with the second layer. For example, the cathode may be described as being “disposed on top” of the anode, even though various organic layers exist between the cathode and the anode.

As used herein, “solution processable” means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.

If the ligand is believed to contribute directly to the photoactive properties of the emitting material, the ligand may be referred to as “photoactive.” A ligand may be referred to as “auxiliary” if the ligand is not believed to contribute to the photoactive properties of the emitting material, although the accessory ligand may alter the properties of the photoactive ligand.

As used herein, and as generally understood by those skilled in the art, a first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” when the first energy level is closer to the vacuum energy level. The (LUMO) energy level is “larger than” or “higher than” the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, higher HOMO energy levels correspond to IPs with smaller absolute values (less negative IPs). Likewise, higher LUMO energy levels correspond to electron affinities (EA) with smaller absolute values (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. “Higher” HOMO or LUMO energy levels appear closer to the top of the diagram than “lower” HOMO or LUMO energy levels.

As used herein, and as generally understood by those skilled in the art, a first work function is “greater than” or “higher” than a second work function if the absolute value of the first work function is greater. Work functions are usually measured as negative numbers relative to the vacuum level, so a “higher” work function is more negative. In a typical energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther down from the vacuum level. Therefore, the definition of HOMO and LUMO energy levels follows a different convention than the work function.

Further details and the preceding definition of OLED can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

There is a need in the art for indolocarbazole and fluorene compounds with improved properties for use in OLEDs. The present invention addresses this need in the art.

According to one embodiment, there is provided a compound having a formula selected from the group consisting of formulas (I), (II) and (III):

Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently selected from benzene, biphenyl, terphenyl, triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzo selected from the group consisting of furan, dibenzothiophene, dibenzoselenophen, and combinations thereof;

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently and optionally further substituted with hydrogen, deuterium, halogen, alkyl, aryl, heteroaryl, cycloalkyl, silyl, and combinations thereof;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent from a single substitution to the maximum possible number of substitutions, or no substitution;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, benzene, biphenyl, terphenyl , triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzofuran, dibenzothiophene, dibenzoselenophen, carbazole, and combinations thereof;

L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently selected from the group consisting of direct bond, alkyl, benzene, biphenyl, terphenyl and combinations thereof;

At least one of Ar ¹ and Ar ² is 9,9-disubstituted fluorene, at least one of Ar ³ and Ar ⁴ is 9,9-disubstituted fluorene, and at least one of Ar ⁵ and Ar ⁶ is 9,9-disubstituted fluorene It is fluorene.

According to another embodiment, an organic light emitting diode/device (OLED) is also provided. The OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may contain a compound of the present invention. According to yet another embodiment, the organic light emitting device may be included in a device selected from a consumer product, electronic component module, and/or lighting panel.

According to another embodiment, the present invention provides a formulation comprising a compound of the present invention.

Figure 1 shows an organic light emitting device.
Figure 2 shows an inverted organic light emitting device without a separate electron transport layer.

Typically, OLEDs include one or more organic layers disposed between and electrically connected to an anode and a cathode. When current is applied, the anode injects holes into the organic layer(s) and the cathode injects electrons. The injected holes and electrons each move toward oppositely charged electrodes. When an electron and a hole become localized on the same molecule, an “exciton” is created, which is a localized electron-hole pair with an excited energy state. When excitons relax through a photoemission mechanism, light is emitted. In some cases, excitons may localize to excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

Early OLEDs used emitting molecules that emit light (“fluorescence”) from a singlet state, as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs have been presented with emitting materials that emit light from the triplet state (“phosphorescence”). Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”)] and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, no. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entirety. Phosphorescence is described more specifically in U.S. Pat. No. 7,279,704 at columns 5-6, which is incorporated by reference.

1 shows an organic light emitting device 100. The drawings are not necessarily drawn to scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, and an electron transport layer. (145), it may include an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers in the order described. The properties and functions of these various layers, as well as example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

More examples for each of these layers are also available. For example, a flexible, transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. It is included as Examples of release and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a 1:1 molar ratio, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes, including compound cathodes with thin layers of metals such as Mg:Ag with laminated transparent, electroconductive sputter-deposited ITO layers. It is done. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

Figure 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emission layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers in the order described. Since the most common OLED configuration is with the cathode disposed above the anode, and device 200 has cathode 215 disposed below the anode 230, device 200 may be referred to as an “inverted” OLED. You can. Materials similar to those described with respect to device 100 may be used in that layer of device 200. Figure 2 provides an example of how some layers may be omitted from the structure of device 100.

The simple stacked structures shown in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the invention may be used in connection with a variety of other structures. The specific materials and structures described are illustrative in nature; other materials and structures may also be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or layers can be omitted entirely based on design, performance and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials may be used, such as mixtures of hosts and dopants, or more generally mixtures. Additionally, the layer may have various sublayers. The names given for the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220 and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an “organic layer” disposed between the cathode and anode. This organic layer may comprise a single layer, or may further comprise a plurality of layers of different organic materials, for example as described in connection with Figures 1 and 2.

OLEDs (PLEDs) comprising structures and materials not specifically described, such as polymeric materials such as those disclosed in U.S. Pat. No. 5,247,190 (Friend et al.), which is incorporated by reference in its entirety, may also be used. As a further example, OLEDs with a single organic layer can be used. OLEDs can be laminated, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can deviate from the simple stacked structures shown in FIGS. 1 and 2. For example, the substrate may have an out-coupled structure such as a mesa structure as described in U.S. Pat. No. 6,091,195 (Forrest et al.) and/or a pit structure as described in U.S. Patent No. 5,834,893 (Bulovic et al.). They may include angled reflective surfaces to improve out-coupling, and these patent documents are incorporated herein by reference in their entirety.

Unless explicitly stated to the contrary, any layer of the various embodiments may be deposited by any suitable method. For the organic layer, preferred methods include thermal evaporation as described in U.S. Pat. Nos. 6,013,982 and 6,087,196 (which are incorporated by reference in their entirety), ink-jet, U.S. Pat. No. 6,337,102 (Forrest et al.) Organic Vapor Deposition (OVPD), as described in U.S. Patent No. 7,431,968, which is incorporated by reference in its entirety, and Organic Vapor Jet Printing (OVJP), which is incorporated by reference in its entirety. Deposition by . Other suitable deposition methods include spin coating and other solution-based processes. The solution-based process is preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred pattern formation methods include deposition through a mask, cold welding as described in U.S. Pat. Includes pattern formation. Other methods may also be used. The material to be deposited can be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, preferably containing three or more carbons, can be used in small molecules to improve their solution processing capability. Substituents having 20 or more carbons can be used, and the preferred range is 3 to 20 carbons. Because asymmetric materials may have a lower tendency to recrystallize, materials with an asymmetric structure may have better solution processability than materials with a symmetric structure. Dendrimer substituents can be used to improve the solution processing ability of small molecules.

Devices fabricated according to embodiments of the present invention may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrode and organic layer from damage due to exposure to harmful species in environments containing moisture, vapors and/or gases, etc. The barrier layer may be deposited over the electrodes, over the substrate, under the substrate, or next to the substrate, over any other part of the device, including the edge. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials can be used in the barrier layer. The barrier layer may include inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials such as those described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are incorporated herein in their entirety. Included for reference. To be considered a “mixture,” the polymeric and non-polymeric materials described above, including the barrier layer, must be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymer to non-polymer material may range from 95:5 to 5:95. Polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated according to embodiments of the present invention may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light emitting devices such as individual light source devices or lighting panels that can be used by end consumer product producers, etc. These electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present invention may be incorporated into a wide variety of consumer products that include one or more electronic component modules (or units) therein. These consumer products may include any type of product that includes one or more light source(s) and/or one or more image displays of some type. Some examples of these consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signal lights, heads-up displays, fully or partially transparent displays, flexible displays, and lasers. Printers, phones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, automobiles, large-area walls, theaters or stadiums. Includes screens or signs. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made according to the present invention. Many devices are intended for use in a temperature range that is comfortable for humans, such as 18°C to 30°C, more preferably at room temperature (20°C to 25°C), but may also be used at temperatures outside this temperature range, such as -40°C to +80°C. It can also be used in

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices, such as organic transistors, can use the materials and structures.

As used herein, the terms “halo,” “halogen,” or “halide” include fluorine, chlorine, bromine, and iodine.

As used herein, the term “alkyl” contemplates both straight or branched chain alkyl radicals. Preferred alkyl groups contain 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, and 3-methylpropyl. -Includes methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl group may be optionally substituted.

As used herein, the term “cycloalkyl” contemplates a cyclic alkyl radical. Preferred cycloalkyl groups contain 3 to 10 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, etc. Additionally, cycloalkyl groups may be optionally substituted.

As used herein, the term “alkenyl” contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Additionally, alkenyl groups may be optionally substituted.

As used herein, the term “alkynyl” contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, alkynyl groups may be optionally substituted.

As used herein, the terms “aralkyl” or “arylalkyl” are used interchangeably and contemplate an alkyl group having an aromatic group as a substituent. Additionally, aralkyl groups may be optionally substituted.

As used herein, the term “heterocyclic group” contemplates aromatic and non-aromatic cyclic radicals. Heteroaromatic cyclic radical also refers to heteroaryl. Preferred heterononaromatic cyclic groups are those containing 3 or 7 ring atoms including one or more heteroatoms, cyclic amines such as morpholino, piperdino, pyrrolidino, etc., and tetrahydrofuran, tetrahydropyran. and cyclic ethers such as the like. Additionally, heterocyclic groups may be optionally substituted.

As used herein, the term “aryl” or “aromatic group” contemplates single ring groups and polycyclic ring systems. A polycyclic ring may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), where, for example, one or more of the rings is aromatic and the other rings are cyclo. It may be alkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Aryl groups with 6, 10 or 12 carbons are particularly preferred. Suitable aryl groups are phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl. , triphenyl, triphenylene, fluorene and naphthalene. Additionally, the aryl group may be optionally substituted.

As used herein, the term “heteroaryl” contemplates a single ring heteroaromatic group that may contain from 1 to 5 heteroatoms. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are common to two adjacent rings (these rings are "fused"), where, for example, one or more of the rings is heteroaryl. and the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups are dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophen, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine. , pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxatia Zine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine , Pteridine, Preferred include dibenzothiophene, dibenzofuran, dibenzoselenophen, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole and aza-analogues thereof. Additionally, heteroaryl groups may be optionally substituted.

Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic groups, aryl and heteroaryl may be unsubstituted or substituted with deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, Amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfur It may be substituted with one or more substituents selected from the group consisting of ponyl, phosphino, and combinations thereof.

As used herein, “substituted” indicates that a substituent other than H is attached to the relevant position, such as carbon. Thus, for example, when R ¹ is monosubstituted, one R ¹ must be other than H. Likewise, when R ¹ is double substituted, two of R ¹ must be other than H. Likewise, when R ¹ is unsubstituted, R ¹ is hydrogen for all possible positions.

The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in each segment may be replaced with a nitrogen atom, e.g. Azatriphenylene includes, but is not limited to, both dibenzo[ f,h ]quinoxaline and dibenzo[ f,h ]quinoline. Those skilled in the art will readily consider other nitrogen analogs of the aza-derivatives described above, all of which are intended to encompass the terms described herein.

When a molecular segment is described as being a substituent or otherwise attached to another moiety, its name is given as if it were the segment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g. For example, benzene, naphthalene, dibenzofuran). As used herein, different designations of such substituents or linked segments are considered equivalent.

Compounds of the invention

Compounds of the present invention can be synthesized using techniques known in the art of organic synthesis. Starting materials and intermediates required for the synthesis may be obtained from commercial sources or according to methods known to those skilled in the art.

Indolocarbazole and fluorene are excellent charge transport building blocks for organic electronic devices. Moreover, they have high triplet energies that can effectively localize excitons on the emitting dopant. In one aspect of the invention, selected indolocarbazoles and fluorenes are combined to synthesize novel compounds for applications in organic electroluminescent devices.

In one aspect, the invention includes compounds having a formula selected from the group consisting of Formulas (I), (II) and (III):

Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently selected from benzene, biphenyl, terphenyl, triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzo selected from the group consisting of furan, dibenzothiophene, dibenzoselenophen, and combinations thereof;

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently and optionally further substituted with hydrogen, deuterium, halogen, alkyl, aryl, heteroaryl, cycloalkyl, silyl, and combinations thereof;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent from a single substitution to the maximum possible number of substitutions, or no substitution;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, benzene, biphenyl, terphenyl , triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzofuran, dibenzothiophene, dibenzoselenophen, carbazole, and combinations thereof;

L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently selected from the group consisting of direct bond, alkyl, benzene, biphenyl, terphenyl and combinations thereof;

At least one of Ar ¹ and Ar ² is 9,9-disubstituted fluorene, at least one of Ar ³ and Ar ⁴ is 9,9-disubstituted fluorene, and at least one of Ar ⁵ and Ar ⁶ is 9,9-disubstituted fluorene It is fluorene.

In one embodiment, the compound is of formula (I). In another embodiment, the compound is of formula (II). In another embodiment, the compound is of formula (III).

In one embodiment, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently selected from hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, benzene, It is selected from the group consisting of biphenyl, terphenyl, triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzofuran, dibenzothiophene, dibenzoselenophen, carbazole, and combinations thereof. . In one embodiment, R ¹ to R ⁹ are each hydrogen.

In one embodiment, L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently selected from the group consisting of direct bond, alkyl, benzene, biphenyl, terphenyl, and combinations thereof. In another embodiment, L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each a direct bond.

In one embodiment, the compound is selected from the group consisting of:

where R ^A and R ^B are each independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, benzene, biphenyl, and combinations thereof,

R ^A and R ^B are randomly connected to form a ring.

In one embodiment, the compound is selected from the group consisting of:

In some embodiments, the compound may be an emissive dopant. In some embodiments, the compound may cause emission by phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also known as E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes.

According to another aspect of the present disclosure, an OLED is also provided. An OLED includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer may include compounds of the invention and modifications thereof as described herein.

OLEDs may be included within one or more of consumer products, electronic component modules, and lighting panels. In some embodiments the organic layer can be the emitting layer and the compound can be the host.

The organic layer may also include an emitting dopant. In some embodiments, two or more emitting dopants are preferred. In one embodiment, the organic layer further includes a phosphorescent emitting dopant. In some embodiments, the emissive dopant is a transition metal complex having one or more ligands or a portion of a ligand, if more than 2 denticles, selected from the group consisting of:

wherein each X ¹ to X ¹³ is independently selected from the group consisting of carbon and nitrogen;

_and

R' and R" are optionally fused or connected to form a ring;

Each R _a , R _b , R _c and R _d may represent from a single substitution to the maximum number of substitutions possible, or no substitution;

R', R", R _a , R _b , R _c and R _d are each independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, selected from the group consisting of cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof become;

Any two adjacent substituents among R _a , R _b , R _c and R _d are optionally fused or linked to form a ring or a multidentate ligand.

Additional information on possible emitting dopants is provided below.

In some embodiments, the organic layer is a blocking layer and the compound of the invention is a blocking material of the organic layer. In other embodiments the organic layer is the transport layer and the compound of the present invention is the transport material of the organic layer.

In another aspect of the disclosure, combinations comprising compounds according to the invention are described. The formulation may include one or more components disclosed herein selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, and electron transport layer materials.

combination with other substances

Materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art will readily consult the literature to identify other materials that may be useful in combination. You can.

Conductive dopants :

The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which will in turn change its conductivity. Conductivity is increased by creating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer. Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with the references disclosing the materials:

EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, 77, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

및

and

HIL/HTL :

The hole injection/transport material to be used in the present invention is not specifically limited, and any compound can be used as long as the compound is commonly used as a hole injection/transport material. Non-limiting examples of substances include phthalocyanine or porphyrin derivatives; Aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorohydrocarbons; polymers with conductive dopants; Conductive polymers such as PEDOT/PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; Metal oxide derivatives such as MoO _x ; p-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; Metal complexes and crosslinkable compounds can be mentioned.

Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the structural formula:

Each of Ar ¹ to Ar ⁹ is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene. A group consisting of; Dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophen, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, Imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadia zine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, Aromatic heterocyclics such as xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine. A group consisting of compounds; and groups of the same type or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are directly attached to oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic cyclic groups. or 2 to 10 cyclic structural units bonded through one or more of these. Each Ar may be unsubstituted or may be deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, hetero It may be further substituted with a substituent selected from the group consisting of aryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar ¹ to Ar ⁹ are independently selected from the group consisting of:

where k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are C (including CH) or N; Z ¹⁰¹ is NAr ¹ , O or S; Ar ¹ has the same group as defined above.

Non-limiting examples of metal complexes used in HIL or HTL include the formula:

wherein Met is a metal and may have an atomic weight greater than 40; (Y ¹⁰¹ -Y ¹⁰² ) is a bidentate ligand, and Y ¹⁰¹ and Y ¹⁰² are independently selected from C, N, O, P and S; L ¹⁰¹ is an auxiliary ligand; k' is an integer value ranging from 1 to the maximum number of ligands that can be bound to the metal; k'+k" is the maximum number of ligands that can be bound to the metal.

In one embodiment, (Y ¹⁰¹ -Y ¹⁰² ) is a 2-phenylpyridine derivative. In another embodiment, (Y ¹⁰¹ -Y ¹⁰² ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In a further aspect, the metal complex has a minimum oxidation potential to Fc ⁺ /Fc couple in solution of less than about 0.6 V.

Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US2006018 2993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, 233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, 205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, O2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, 0921, WO2014034791, WO2014104514, WO2014157018.

EBL:

An electron blocking layer (EBL) can be used to reduce the number of electrons and/or excitons leaving the emitting layer. The presence of such a blocking layer in a device can lead to significantly higher efficiency, and/or longer lifetime compared to a similar device without the blocking layer. Additionally, a blocking layer can be used to localize emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum) and/or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in the EBL contains the same used molecule or the same used functional group as one of the hosts described below.

Host:

The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. The table below categorizes host materials as preferred for devices emitting various colors, but any host material may be used with any dopant as long as it meets the triplet criteria.

Examples of metal complexes used as hosts preferably have the following formula:

where Met is a metal; (Y ¹⁰³ -Y ¹⁰⁴ ) is a bidentate ligand, and Y ¹⁰³ and Y ¹⁰⁴ are independently selected from C, N, O, P and S; L ¹⁰¹ is another ligand; k' is an integer value ranging from 1 to the maximum number of ligands that can be bound to the metal; k'+k" is the maximum number of ligands that can be bound to the metal.

이며, 여기서 (O-N)은 원자 O 및 N에 배위 결합된 금속을 갖는 2좌 리간드이다.In one aspect, the metal complex is

, where (ON) is a bidentate ligand with a metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y ¹⁰³ -Y ¹⁰⁴ ) is a carbene ligand.

Examples of organic compounds used as hosts include aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, The group consisting of perylene and azulene; Aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophen, carbazole, indolocarbazole, pyridylindole, p. Rolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine , oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, Phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenope. The group consisting of nodipyridine; and groups of the same type or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are directly attached to oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic cyclic groups. or is selected from the group consisting of 2 to 10 cyclic structural units bonded by one or more of these. Each option within each group may be unsubstituted or may be deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, may be substituted with a substituent selected from the group consisting of aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound includes one or more of the following groups in the molecule:

Here, R ¹⁰¹ to R ¹⁰⁷ are each independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, selected from the group consisting of aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof, and if aryl or heteroaryl, the above description It has a similar definition to Ar. k is an integer from 0 to 20 or 1 to 20; k"' is an integer from 0 to 20. X ¹⁰¹ to X ¹⁰⁸ are selected from C (including CH) or N.

Z ¹⁰¹ and Z ¹⁰² are selected from NR ¹⁰¹ , O or S.

The non -limiting example of the host material that can be used in OLED in combination with the substance disclosed herein is exemplified with the reference document that discloses the material: EP2034538, EP2034538A , KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090 309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, 01446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, 063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472.

Emitter:

Emitter examples are not particularly limited, and any compound may be used as long as the compound is commonly used as an emitter material. Examples of suitable emitter materials include those that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e. TADF (also referred to as E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes. Including, but not limited to, compounds that are present.

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with references disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155. , EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670 , US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, 70111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, 80233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930 , US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100 295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, 85275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190 , US2013334521, US20140246656, US2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US7332232, US73 78162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, WO06081973, WO06121811, WO07018067 , WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, , WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, 044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620 , WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.

HBL:

A hole blocking layer (HBL) can be used to reduce the number of holes and/or excitons leaving the emission layer. The presence of such a blocking layer in a device can lead to significantly higher efficiency and/or longer lifetime compared to a similar device without the blocking layer. Additionally, a blocking layer can be used to localize emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (further from vacuum level) and/or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from vacuum level) and/or a higher triplet energy than one or more of the hosts closest to the HBL interface.

In one embodiment, the compound used in HBL comprises the same used molecule or the same used functional group as the host described above.

In another embodiment, the compounds used in HBL include one or more of the following groups in the molecule:

where k is an integer from 1 to 20; L ¹⁰¹ is another ligand and k' is an integer from 1 to 3.

ETL:

The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer can be native (undoped) or doped. Doping can be used to improve conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used as long as they are conventionally used to transport electrons.

In one embodiment, the compound used in ETL contains one or more of the following groups in the molecule:

Here, R ¹⁰¹ is hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl , carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and if aryl or heteroaryl, has a similar definition to Ar as described above. have Ar ¹ to Ar ³ have similar definitions to Ar described above. k is an integer from 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are selected from C (including CH) or N.

In another embodiment, metal complexes used in ETL include, but are not limited to, the formula:

where (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L ¹⁰¹ is another ligand; k' is an integer value ranging from 1 to the maximum number of ligands to which the metal can be bound.

Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are illustrated below along with the references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918 , JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090 179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, , US8415031, WO2003060956, WO2007111263, WO2009148269 , WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535.

Charge generation layer (CGL):

In tandem or stacked OLEDs, the CGL plays an essential role in performance and consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; Afterwards, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conducting dopants used in the transport layer.

In any of the above-described compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Accordingly, any specifically listed substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., may be in its non-deuterated, partially deuterated and fully deuterated forms. Likewise, substituent types such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc. may also be in their deuterated, partially deuterated and fully deuterated forms.

[Experiment]

material synthesis

Chemical abbreviations used throughout this document are:

Pd ₂ (dba) ₃ : tri(dibenzylideneacetone) dipalladium (0)

SPhos: Dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine

DCM: dichloromethane

Synthesis of compound HA1

5-phenyl-5,12-dihydroindolo[3,2- a ]carbazole (3.3 g, 9.93 mmol), 2-bromo-9,9-dimethyl-9 H in xylene (120 mL) A solution of fluorene (3.66 g, 13.40 mmol), tert -BuONa (1.908 g, 19.86 mmol), Pd ₂ (dba) ₃ (0.091 g, 0.099 mmol) and SPhos (0.082 g, 0.199 mmol) was grown under nitrogen for 16 h. It was refluxed under The solvent was evaporated and the residue was purified by column chromatography on silica gel using heptane/DCM (6/4, v/v) as eluent. The crude product was recrystallized from heptane/DCM and toluene/ethanol to give compound HA1 (1.9 g, 36%) as a white solid.

Synthesis of compound HA2

Following the procedure for the synthesis of compound HA1, 5-([1,1'-biphenyl]-4-yl)-5,12-dihydroindolo[3,2- a ]carbazole and 2-bromo- Compound HA2 was synthesized from 9,9-dimethyl-9 H -fluorene. Compound HA2 was synthesized in 64% yield as a white solid.

Synthesis of compound HA9

5-(dibenzo[b,d]furan-3-yl)-5,12-dihydroindolo[3,2- a ]carbazole and 2-bromo-9 following the procedure for the synthesis of compound HA1. Compound HA9 was synthesized from ,9-dimethyl-9 H -fluorene. Compound HA9 was synthesized in 82% yield as a white solid.

Synthesis of compound HA22

5,12-dihydroindolo[3,2- a ]carbazole (2.25 g, 8.78 mmol), 2-bromo-9,9-dimethyl-9 H -fluorene (7.19) in xylene (100 ml) g, 26.3 mmol), Pd ₂ (dba) ₃ (0.11 g, 0.12 mmol), SPhos (0.12 g, 0.29 mmol) and tert -BuONa (3.37 g, 35.1 mmol) were refluxed under nitrogen for 12 hours. After cooling to room temperature, the solvent was evaporated. The residue was purified by column chromatography on silica gel using heptane/DCM (7/3 to 3/2, v/v) as eluent and recrystallized from ethanol to give compound HA22 (2.8 G, 50%) as white crystals. got it

Synthesis of compound HA27

Following the procedure for the synthesis of compound HA1, 5-(9,9-dimethyl-9 H -fluoren-2-yl)-5,12-dihydroindolo[3,2- a ]carbazole and 4-bro Compound HA27 was synthesized from parent-1,1'-biphenyl. Compound HA27 was synthesized in 94% yield as a white solid.

Synthesis of compound HA28

Following the procedure for the synthesis of compound HA1, 5-(9,9-dimethyl-9 H -fluoren-2-yl)-5,12-dihydroindolo[3,2- a ]carbazole and 3-bro Compound HA28 was synthesized from parent-1,1'-biphenyl. Compound HA28 was synthesized in 92% yield as a white solid.

Synthesis of compound HB2

Following the procedure for the synthesis of compound HA1, 5-([1,1'-biphenyl]-4-yl)-5,8-dihydroindolo[2,3- c ]carbazole and 2-bromo- Compound HB2 was synthesized from 9,9-dimethyl-9 H -fluorene. Compound HB2 was synthesized in 70% yield as a white solid.

Synthesis of compound HB17

Compound HB17 was synthesized from 5,8-dihydroindolo[2,3- c ]carbazole and 2-bromo-9,9-dimethyl-9 H -fluorene following the procedure for the synthesis of compound HA22. Compound HB17 was synthesized in 84% yield as a white solid.

Application example in OLED

All devices were fabricated by high vacuum (~ 10 ^-7 Torr) thermal evaporation. The anode electrode was 80 nm of indium tin oxide (ITO). The cathode electrode consisted of 1 nm of LiF followed by 100 nm of Al. All devices were encapsulated in a glass lid sealed with epoxy resin in a nitrogen glove box (<1 ppm of H ₂ O and O ₂ ) immediately after fabrication, and a moisture getter was introduced into the package.

Device embodiment

One set of device examples includes, sequentially from the ITO surface, 10 nm of LG101 (manufactured by LG Chem) as the hole injection layer (HIL), 45 nm of PPh-TPD as the hole transport layer (HTL), and 40 nm of the emission layer (EML). ) and then an organic layer consisting of 35 nm of aDBT-ADN with 35 wt% LiQ as the electron transport layer (ETL). EML has three components, 50 wt% of EML is the inventive compound (HA2 or HB2) or comparative compound (CC-1 or CC-2) as the first host; 40 wt% of EML is compound EH-1 as the second host; 10 wt% of EML was compound GD as emitter. The structures of the compounds used are shown below.

Table D1 below provides a summary of the device data reported at 1000 nits for the device examples. Relative lifetime (LT97, arbitrary units, AU), defined as the time it takes for a device to decay to 97% of its original luminescence under constant drive current density giving an initial luminescence of 1000 nits, assuming an acceleration factor of 1.8 Thus, it is calculated from the measured values recorded at 40 mA/cm ² and normalized to that of device C-1.

[Table D1]

The data in Table D1 shows that devices using compounds of the invention as the first host achieve longer lifetimes than devices using comparative compounds as the first host. The only difference between the compounds of the invention and the comparative compounds is that the compounds of the invention have a fluorene moiety replacing one of the biphenyl moieties of the comparative compounds, and this appears to be crucial in improving the performance of the materials. Pay attention to

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may therefore include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to how the invention operates are not intended to be limiting.

Claims (15)

A material for OLED comprising a compound having a chemical formula selected from the group consisting of the following formulas (I), (II) and (III):

Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently selected from benzene, biphenyl, terphenyl, triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzo selected from the group consisting of furan, dibenzothiophene, dibenzoselenophen, and combinations thereof;
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently and optionally further substituted with hydrogen, deuterium, halogen, alkyl, aryl, heteroaryl, cycloalkyl, silyl, and combinations thereof;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent from a single substitution to the maximum possible number of substitutions, or no substitution;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, benzene, biphenyl, terphenyl , triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzofuran, dibenzothiophene, dibenzoselenophen, carbazole, and combinations thereof;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently selected from the group consisting of a direct bond, alkyl, benzene, biphenyl, terphenyl, and combinations thereof, provided that L ¹ , L When ² , L ³ , L ⁴ , L ⁵ or L ⁶ is benzene, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ or Ar ⁶ connected thereto is not dibenzothiophene;
At least one of Ar ¹ and Ar ² is 9,9-disubstituted fluorene, at least one of Ar ³ and Ar ⁴ is 9,9-disubstituted fluorene, and at least one of Ar ⁵ and Ar ⁶ is 9,9-disubstituted fluorene It is fluorene, and the 9,9-disubstituted fluorene does not have a substituent containing a hetero atom. 2. The material according to claim 1, which is a compound of formula (I). 2. The material according to claim 1, which is a compound of formula (II). 2. The material according to claim 1, which is a compound of formula (III). The material of claim 1, wherein R ¹ to R ⁹ are each hydrogen. The material of claim 1, wherein the compound is selected from the group consisting of the following formula:

where R ^A and R ^B are each independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, benzene, biphenyl, and combinations thereof,
R ^A and R ^B are randomly connected to form a ring. The material of claim 1, wherein L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each a direct bond. The material of claim 1, wherein the compound is selected from the group consisting of the following formula:

An organic layer comprising a compound having a formula selected from the group consisting of the following formulas (I), (II) and (III):

Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently selected from benzene, biphenyl, terphenyl, triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzo selected from the group consisting of furan, dibenzothiophene, dibenzoselenophen, and combinations thereof;
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently and optionally further substituted with hydrogen, deuterium, halogen, alkyl, aryl, heteroaryl, cycloalkyl, silyl, and combinations thereof;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent from a single substitution to the maximum possible number of substitutions, or no substitution;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, benzene, biphenyl, terphenyl , triphenylene, fluorene, benzofuran, benzothiophene, benzoselenophen, dibenzofuran, dibenzothiophene, dibenzoselenophen, carbazole, and combinations thereof;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are each independently selected from the group consisting of a direct bond, alkyl, benzene, biphenyl, terphenyl, and combinations thereof, provided that L ¹ , L When ² , L ³ , L ⁴ , L ⁵ or L ⁶ is benzene, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ or Ar ⁶ connected thereto is not dibenzothiophene;
At least one of Ar ¹ and Ar ² is 9,9-disubstituted fluorene, at least one of Ar ³ and Ar ⁴ is 9,9-disubstituted fluorene, and at least one of Ar ⁵ and Ar ⁶ is 9,9-disubstituted fluorene It is fluorene, and the 9,9-disubstituted fluorene does not have a substituent containing a hetero atom. 10. The organic layer according to claim 9, wherein the organic layer is an emitting layer and the compound of formula (I), (II) or (III) is the host. 10. The method of claim 9, wherein the organic layer further comprises a phosphorescent emitting dopant; Here, the emitting dopant, when the ligand is more than two denticles, is an organic layer that is a transition metal complex having at least one ligand or part of a ligand selected from the group consisting of the following formula:


wherein each X ¹ to X ¹³ is independently selected from the group consisting of carbon and nitrogen;
_and
R' and R" are optionally fused or connected to form a ring;
Each R _a , R _b , R _c and R _d may represent from a single substitution to the maximum number of substitutions possible, or no substitution;
R', R", R _a , R _b , R _c and R _d are each independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, selected from the group consisting of cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof become;
Any two adjacent substituents among R _a , R _b , R _c and R _d are optionally fused or linked to form a ring or a multidentate ligand. 10. The organic layer according to claim 9, wherein the organic layer is a blocking layer and the compound of formula (I), (II) or (III) is a blocking material of the organic layer. 10. The organic layer according to claim 9, wherein the organic layer is a transport layer and the compound of formula (I), (II) or (III) is a transport material of the organic layer. 10. The organic layer of claim 9, wherein the organic layer is comprised in a device selected from the group consisting of consumer products, electronic component modules, and lighting panels. delete

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